Pyrotechnic disseminating formulation

ABSTRACT

The invention is a novel pyrotechnic disseminating composition employing aminoguanidinium nitrates or condensation products of aminoguanidinium nitrates as a fuel, inorganic oxidizers which readily are combustible at atmospheric pressures as oxidizer and effective quantities of an agent to be disseminated.

United States Patent Niles 1 Sept. 30, 1975 PYROTECHNIC DISSEMINATING FORMULATION [75] Inventor: Earl Thomas Niles, Midland, Mich.

[731 Assignee: The Dow Chemical Company,

Midland, Mich.

[22] Filed: Nov. 21, 1966 [21] Appl. No: 596,009

[52] US. Cl. 149/76; 149/75; 149/78; 149/83; 149/84; 149/85 [51] Int. Cl. G06B 29/22 [58] Field of Search 149/36, 75, 76, 77, 78,

[56] References Cited UNITED STATES PATENTS 3.335,039 8/1967 Niles et al 149/76 3,335,040 8/1967 Niles..... 149/76 Primary E.\'alniner Stephen J. Lechcrt, Jr. Attorney, Agent, or FirmLloyd S. Jowanovitz [57] ABSTRACT The invention is a novel pyrotechnic disseminating composition employing aminoguanidinium nitrates or condensation products of aminoguanidinium nitrates as a fuel, inorganic oxidizers which readily are combustible at atmospheric pressures as oxidizer and effective quantities of an agent to be disseminated.

6 Claims, N0 Drawings PYROTECHNIC DISSEMINATING FORMULATION This invention relates to pyrotechnic dissemination and more particularly is concerned with disseminating systems based on novel pyrotechnic fuel formulations employing aminoguanidinium nitratesalts as a fuel.

Pyrotechnic disseminating formulations are widely employed for colored smoke production used as a signal or screen, for the distribution of plant growth regulating agents such as pesticides, fumigants, herbicides and the like and for the release and distribution of chemicals used in warfare and law enforcement such as tear gas, psychotomimetic incapacitating agents and the like.

The primary problem in disseminating such signalling and treating materials, hereinafter referred to as agents, by pyrotechnic means is in providing a combustible mixture evolving large quantities of gaseous combustion products which burns at a sufficiently low temperature such that the agent being disseminated is not detrimentally degraded or destroyed. In general, such compositions should provide large volumes of gaseous combustion products while undergoing complete burning at a low burning pressure, eg a maximum of about two atmospheres, and a maximum burning temperature of about 800 C. and preferably from about 300 to about 600 C. It is another criterium of operation that the agent to be disseminated must be compatible with the pyrotechnic composition to assure reliability of burning after storage as well as storageability without mix degradation.

Heretofore, pyrotechnic dissemination of smoke dyes, herbicides, chemical warfare materials, tear gas and other like agents has been carried out using compositions wherein substantial amounts of the agent to be disseminated are mixed with cool burning fuel oxidizer combinations which provide copious quantities of water vapor and carbon dioxide as the principal gaseous exhaust products. In these formulations, many times undesirable high percentages of the agent are lost through degradation during the combustion dissemination process.

Empirically, it has been found that a mixture of carbohydrates or sulfur with potassium chlorate in the presence of minor amounts of certain additives e.g. sodium bicarbonate with sulfur or kaolin with sugar, can be used as a pyrotechnic system for dissemination of colored smoke and chemical warfare agents. These systems can be classified as cool burning only because of the flame quenching additives employed therein. Polyvinyl acetate in dilute solutions has been used with these conventional pyrotechnic compositions to increase their physical strength and ease of consolidation. Such solutions reduce the amount of pressure needed to compact the formulations into a grain. This is of interest especially with those formulations containing sulfur as compaction of such formulations at high pressure is hazardous in that these compositions during fabrication are prone to ignition. Even when partially compacted, the resulting deflogration borders on detonation with respect to velocity. Oil, as a diluent, has been used to moisten and reduce friction sensitivity in such mixtures. This material, however, undesirably degrades the composition from the standpoint of efficiency of dissemination.

Dissemination of agents of the type set forth herein also has been realized using pyrochemical gas producers as the high volume gas source. To illustrate, selfsustained gas producing reactions as realized by the relatively low temperature catalytic decomposition of ammonium nitrate, guanidine nitrate and nitroguanidine utilizing chromates and dichromates as catalysts have been used to disperse benzene hexachloride, DDT and other pesticides. These formulations suffer from the disadvantage that they exhibit relatively low efficiency of dissemination and are not universally applicable.

It is a principal object of the present invention to provide a novel pyrotechnic composition for dissemination of smoke dyes, pesticides, chemical warfare and the like agents.

It is also an object of the present invention to provide a pyrotechnic formulation which is safe to handle during mixing and other production operations when in admixture with an agent to be disseminated.

It is a further object of the present invention to provide a pyrotechnic formulation containing an agent to be disseminated wherein the resultant composition remains stable under prolonged storage'even at relatively elevated temperatures of C. or more and which gives high efficiencies of gaseous combustion production and agent dissemination upon use.

It is another object of the present invention to provide a pyrotechnic composition suitable for use with a wide variety of agents ordinarily dispersed by pyrotechnic dissemination.

It is also an object of the present invention to provide a cool-burning pyrotechnic composition for dissemination of agents which requires no coolant additives.

These and other objects and advantages readily will become apparent from the detailed description of the invention presented hereinafter.

The present invention comprises a pyrotechnic disseminating composition employing aminoguanidinium nitrates or condensation products of aminoguanidinium nitrates as a fuel, inorganic oxidizers which readily are combustible at atmospheric pressures as oxidizer and effective quantities of an agent to be disseminated.

More particularly, the present invention comprises from about 12 to about 40 weight percent of monoaminoguanidinium nitrate (hereinafter designated as MAG.HNO diaminoguanidinium nitrate (designated as DAG.HNO triaminoguanidinium nitrate (coded as TAG.HNO ethylenebis- (aminoguanidinium) dinitrate (hereinafter referred to as EDM-III-2HNO l-amino-2,5-hydrazinotriazol nitrate (designated as ADHT.HNO 1-amino-2,5- hydrazinotriazol dinitrate (ADHT.2HNO and condensation products of these compounds, from about 8 to about 30 weight percent of an alkali metal or ammonium chlorate or perchlorate such as, for example, sodium chlorate (NaClO potassium chlorate (KClO or ammonium perchlorate (NH ClO and balance, agent to be disseminated.

A preferred embodiment of the present invention comprises from about 19 to about 35 weight percent of monoaminoguanidinium nitrate, triaminoguanidinium nitrate or ethylenebis(aminoguanidinium) dinitrate, from about 8 to about 26 weight percent potassium chlorate, and balance agent to be disseminated.

These formulations exhibit a satisfactory burning rate, are cool burning and develop copious quantities of neutral (i.e. substantially non-reactive with agent) gaseous combustion products to provide good agent dissemination. If desired, however, optionally up to about percent by weight, preferably from about 0.2 to about 2 weight percent of a combustion catalyst, e.g. chromates, copper salts, platinum, rhodium or iridium metals, ferrocene, metal chromites, ferric oxide and the like can be incorporated into the formulation. Alkali metal chromates, e.g. potassium chromate (K CrO and copper halides, e.g. copper chloride, copper chromite and ferric oxide (Fe O have been found to be particularly suitable catalysts. With the catalyst, sustained combustion is realized at stoichiometric or fuel rich fueloxidizer proportions. If the catalyst is not employed, the composition usually must be oxidizer rich to obtain sustained combustion. In some instances, this can lead to undesirable agent degradation during the combustion dissemination process. Additionally, the catalyst provides increased burning rates and increased gaseous combustion product yield and efficiency of agent dissemination.

Agents for dissemination which can be incorporated into the formulation include for example organic dyes such as methylaminoanthraquinone (MAAQ) used for the production of colored smoke, the condensation product of chlorobenzaldehyde and malononitrile commonly employed as a tear gas and hereinafter designated as CS, incapacitating agents which are psychotomimetics such as the classified materials having unclassified U.S. Government code designations B2 and EA- 3443, herbicides, fungicides, pesticides and the like.

By effective quantities of such agents is meant those amounts whereby a predetermined level of treatment or activity is'realized as is understood by one skilled in the art of pyrotechnic dissemination.

The formulations can be fabricated into compacts or grains using techniques and procedures commonly employed in the art. Blends usually are made by mixing the components, placing the resulting substantially h0- mogeneous mix into a container, compacting the mix in the container and contacting the so-compacted formulation with an ignition system and igniter.

Internal burning grains are prepared by pressing or compacting the blend around a mandrel of predetermined shape and size.

The present novel pyrotechnic disseminating formulation offers the unexpected advantages of safety during mixing with agents that are somewhat hazardous to handle in the presence of sulfur. Also, they provide unexpectedly high stability during storage as well as higher efficiency of dissemination when compared with formulations based on conventional pyrotechnic systems.

The following Examples will serve to further illustrate the present invention but are not meant to limit it thereto.

EXAMPLE 1 For aerosol evaluation, a large number of formulations were prepared by mixing a fuel and catalyst (if catalyst was employed), incorporating an agent into the system followed by oxidizer. The resulting formulation, totalling 10 grams, was mixed remotely in a revolving bottle to provide a substantially homogeneous blend. The so-blended pyrotechnic disseminating composition was placed in a small metal can 1.125 inches diameter by 2.25 inches high) and compacted by an applied pressure of about 1500 pounds per square inch. The cover of the can was pierced to providean 0.25 inch opening. A MIL SPEC No. 508 First Fire and a No. 565 Squib igniter was inserted into the can through this opening and placed in contact with the dissemination formulation.

The so-pressed end burning grain was ignited and burning characteristics, including ease of ignition, burning time, combustion temperature and pressure were recorded. Additionally, the aerosol yield,

Agent in Aerosol Form X Aerosol yield Total Weight Composition and Efficiency,

Agent in Aerosol Form X 100 Emclency Agent in Composition also were measured.

' Table I Fuel KC 10;, Oxidizer K CrO Catalyst Comp. Parts by Weight Parts by Weight Parts by Weight No. Component Operable Optimum Operable Optimum Operable Optimum mm. max. min. max. min. max. min. max. min. max. min. max

Control Guanidinium Nitrate 28.1 37 12.6 l8.9 O la MAG.HNO 14.6 37.5 IO 29 0 l0 lb MAG.HNO 24 34 15 25 0.2 2 2a MAG.HNO:, 15 40 1O 3O 0 l0 2b MAGHNO I9 31 ll 0.2 2 3 MAGHNO 28.5 34.5 15.5 21.5 O l 4a EDM-III. I7 35 10 23 0 l0 2l-INO 4b EDM-lll. 28 l ZHNOa 7 0.2 2 5a TAG.HNO;, l9 37 8 30 0 l0 5b TACLHNO 28 35 8 28 0.2 2

6 lyst-S weight percent and MAAQ agent-50 weight percent.

A ent This formulation had a burning time of about 58 secg n C Paris y gK onds, and exhibited acom'bust'ion pressure evaluated as I o omponem g ranging from Low to Medium. The measured Efficiency was about 55 percent and the Aerosol yield was f $2282: 32 2% about 28 percent; T he mix compatibility generally was 2! h 1b 50 55 rated as Good. 2a CS 40 70 2b cs 4s 65 EXAMPLE 4. 3 BZ"'" 34 49 l 4a MAAQ" 50 60 Following the procedure set'forth in Example 1, a

ill 7 1 i $228. Q} 5; 50 number of pyrotechnic disseminating formulations, 5b MAAQ" 50 57 within the composition ranges set forth herein, were fabricated from ethylenebis(aminoguanidinium) dini- IMethylaiminounthruquinonc trate and without Condensation product of chlorobenzuldehyde and mulononitrile 1 "U.S. Government code designated psychotomirnctric agent K2Cr04 as a Combusnon Fatalyst or p System not optimized These were tested for resistance to impact, spark, fric- Table II Compatibility Burning Combustion Combus- Ignition Aerosol Time Temperature tion Character- Yield Efficiency G Comp. sec. C Pressure istics lm- Fric- Surveiler- No. (range) (range) (range) (range) (range) pact Spark tion lance al Control 40-147 200-340 P/M P 13-19.5 25.5-47.5 G G G la 10-60 400- 450 L/G P/G 24-33 39-65 G G G G lb 10-13 400-450 G G 34-36 66-68 G G G G 2a 8-90 400-- 450 L/G P/G -65 30-100 G G G G G 2b 10-20 400-450 G G 46-53 62-86 G G G G G 3 17.5-51 280-540 G G G G G G G 4a 16- 57 300-590 L/M P/G 29-34 58-65 G G G G 4b 27 430 M/G G 33 65 5a 10-30 350-550 L/G P/G 25-36 45-70 G G G G 5b 10-13 440 M/G G 34-37 68-69 G G G G P=Ponr, L==Low, F=Fair. M=Medium, G=Good (Based on Poor as minimal acceptable performance for use in agent dissemination] Formulation compatibility after long term (9-12 weeks) storage at about 70 C.

EXAMPLE 2 Following the same procedure as set forth in Example 1, a number of specific formulations were blended and pressed into grains for aerosol evaluation. Additionally, several disseminating formulations were fabricated into internal burning grains by pressing a substantially homogeneous mixture around a A: inch mandrel.

These were ignited using the igniter system described in Example 1 and the combustion characteristics noted.

The composition of the formulation and combustion characteristics are summarized in Table III.

tion and given a surveillance test as described for Example I. In all of these studies these were rated as Good. The general compatibility exhibited by the formulation also was Good.

A composition of TAGJ-INO, KClO K CrO and B2 similarly showed up as Good in these same tests.

In a manner similar to that described for the foregoing experiments, pyrotechnic disseminating formulations having herbicides, fungicides, and the like pesticides incorporated therein can be prepared using the fuel and oxidizer systems disclosed herein. It is to be understood that combustion catalysts, e. g. copper chlo- Table III Combustion Characteristics Combus- Formulation Burning tion Aerosol Run Fuel KClO K,Cr0., 7 Agent Time Temp. Yield Efficiencies No. Type (g.) (g.) (g) Type (g) (sec) 0 (70) (921) Remarks 1 MAG.- 2.92 1.77 0.11 MAAQ 5.20 11 410 35.5 68

HNO, 2 MAG 20.5 17.5 1.0 CS 61.0 14 380 49.0 80.3

HNO 3 MAG?- 20.5 17.5 1.0 CS 61.0 11 355 811 internal Burn- HNO ing Grain 4 TAGJ-lNO 3.15 1.5 0.10 MAAQ 5.25 13 440 36 68 S TACLHNQ', 16.5 19.0 2.0 CS 62.5 15.5 360 49.5 79

EXAMPLE 3 ride, platinum, copper chromite, rhodium, iridium, so-

dium dichromate, chromic acid. (CrO and the like, as

Following the procedure set forth in Example 1, a 10 disclosed herein alternatively can be utilized in these gram end burning grain was formulated from the following composition: MAGHNO -25 weight percent, NH ClO.,-20 weight percent, F6203 combustion catacompositions.

Various modifications can be made in the present in= vention without departing from the spirit or scope 7, thereof for it is understood that 1 limit, rnyself onlyas defined in the appended claims.

lclaim: a :i; v l. A pyrotechnic disseminating formulation comprismember selected from. the group consisting of aminoguanidinium nitrates and aminoguanidinium a. from about 8 to about 40lweight percent of a fuel 3. The composition as defined in claim 1 wherein the fuel member ranges from about 19 to about 35 weight percent and the oxidizer ranges from about 8 to about 26 weight percent, said fuel member being selected from the group consisting of monoaminoguanidinium nitrate, triaminoguanidinium nitrate and ethylenebis- (aminoguanidinium) dinitrate and said oxidizer being a member selected from the group consisting of potassium chlorate and ammonium perchlorate.

4. The composition as defined in claim 3 wherein the oxidizer is potassium chlorate.

5. The composition as defined in claim 3 and including from about 0.2 to about 2 weight percent of a combustion catalyst.

6. The composition as defined in claim 5 wherein the combustion catalyst is a member selected from the group consisting of potassium chromate and ferric oxide. 

1. A PYROTECHNIC DISSEMINATING FORMULATION COMPRISING A. FROM ABOUT 8 TO ABOUT 40 WEIGHT PERCENT OF A FUEL MEMBER SELECTED FROM THE GROUP CONSISTING OF AMINOGUANIDINIUM NITRATES AND AMINOGUANIDINIUM NITRATE CONDENSATION PRODUCTS, B. FROM ABOUT 8 TO ABOUT 30 PERCENT OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL OR AMMONIUM CHLORATES AND PERCHORATES AS OXIDIZER, AND C. BALANCE AN EFFECTIVE AMOUNT OF AN AGENT SELECTED FROM THE GROUP CONSISTING OF CHEMICAL WARFARE AGENTS, INCAPACITATING AGENTS, SMOKE DYES AND PLANT GROWTH REGULANTS TO BE DISSEMINATED
 2. The composition as defined in claim 1 and including up to about 10 weight percent of a combustion catalyst.
 3. The composition as defined in claim 1 wherein the fuel member ranges from about 19 to about 35 weight percent and the oxidizer ranges from about 8 to about 26 weight percent, said fuel member being selected from the group consisting of monoaminoguanidinium nitrate, triaminoguanidinium nitrate and ethylenebis(aminoguanidinium) dinitrate and said oxidizer being a member selected from the group consisting of potassium chlorate and ammonium perchlorate.
 4. The composition as defined in claim 3 wherein the oxidizer is potassium chlorate.
 5. The composition as defined in claim 3 and including from about 0.2 to about 2 weight percent of a combustion catalyst.
 6. The composition as defined in claim 5 wherein the combustion catalyst is a member selected from the group consisting of potassium chromate and ferric oxide. 